Iron-catalyzed metathesis polymerization of olefins

Abstract

This invention is directed to iron-based complexes, and uses thereof for catalytic olefin metathesis reaction, including ring opening metathesis polymerization of olefins.

What is claimed is: 
     
         1 . An iron complex represented by the structures of formula A1, its dimer A2 or its isomers: 
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  are each independently linear or branched alkyl, cycloalkyl, aryl, heterocyclyl, alkylcycloalkyl, alkylaryl, or alkylheterocyclyl; 
         R 3  is H, D, linear or branched alkyl; 
         R 4  is SiH x (alkyl) y (aryl) z  or CH x (alkyl) y (aryl) z ; wherein x is an integer between 0-3; y is an integer between 0-3; z is an integer between 0-3; wherein x+y+z is 3; 
         Q 1 , Q 2 , Q 3 , Q 4  Q 5  or Q 6  are each independently H, linear or branched alkyl, aryl, heterocyclyl, alkylcycloalkyl, alkylaryl, alkylheterocyclyl, halide, nitro, amide, ester, cyano, alkoxy, NH 2 , aminoalkyl or arylamino; 
         wherein at least one of Q 1 -Q 5  is an alkyl; and 
         n is an integer between 1 and 3. 
       
     
     
         2 . The iron complex of  claim 1 , wherein the iron is iron (III). 
     
     
         3 . The iron complex of  claim 1 , wherein the R 1  and R 2  are the same; or wherein R 1  and R 2  are each independently isopropyl, ethyl, phenyl or tertbutyl; or
 wherein R 3  is H; or wherein R 4  is Si(CH 3 ) 3  or C(CH 3 ) 3 ; or wherein Q2 and Q4 are H; or   wherein Q1, Q3 and Q5 are each independently isopropyl or tertbutyl; or wherein Q 1 , Q 5  are each independently isopropyl or tertbutyl and Q 3  is H.   
     
     
         4 - 9 . (canceled) 
     
     
         10 . The iron complex of  claim 1 , wherein the structure of formula A1 and A2 are in equilibrium in solution. 
     
     
         11 . (canceled) 
     
     
         12 . The iron complex of  claim 1 , wherein the complex is represented by the following structures: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         13 . A method for metathesis polymerization of cyclic olefins comprising reacting a substituted or unsubstituted cyclic olefin with the iron complex of  claim 1 , thereby obtaining a polymer by ring opening metathesis polymerization. 
     
     
         14 . The method of  claim 13 , wherein the cyclic olefin has a strain in the ring; or wherein the cyclic olefin comprises norbornene, bicycles, 3, 4 or 5 membered ring; or wherein the cyclic olefin is a carbocycle or heterocycle; or wherein the cyclic olefin is a diene. 
     
     
         15 - 22 . (canceled) 
     
     
         23 . The method of  claim 13 , wherein the cyclic olefin is substituted or unsubstituted norbornene obtaining a substituted or unsubstituted polynorbornene of formula I: 
       
         
           
           
               
               
           
         
         wherein Q 7  is H, linear or branched alkyl, aryl, heterocyclyl, alkylcycloalkyl, alkylaryl, Si(alkyl) 3 , alkylheterocyclyl, halide, nitro, amide, ester, cyano, alkoxy, NH 2 , aminoalkyl or arylamino; 
         o is an integer between 1-3; 
         m is an integer larger than 2. 
       
     
     
         24 . (canceled) 
     
     
         25 . An iron complex represented by the structures of formula A3 or its isomer: 
       
         
           
           
               
               
           
         
         wherein: 
         R 1  and R 2  are each independently linear or branched alkyl, cycloalkyl, aryl, heterocyclyl, alkylcycloalkyl, alkylaryl, or alkylheterocyclyl; 
         R 3  is H, D, linear or branched alkyl; 
         X 1  and X 2  are each independently Cl, Br, I or F; 
         Q 1 , Q 2 , Q 3 , Q 4 , Q 5  or Q 6  are each independently H, linear or branched alkyl, aryl, heterocyclyl, alkylcycloalkyl, alkylaryl, alkylheterocyclyl, halide, nitro, amide, ester, cyano, alkoxy, NH 2 , aminoalkyl or arylamino; 
         wherein at least one of Q 1 -Q 5  is alkyl; and 
         n is an integer between 1 and 3. 
       
     
     
         26 . The iron complex of  claim 25 , wherein the iron is iron (II). 
     
     
         27 . The iron complex of  claim 25 , wherein the R 1  and R 2  are the same; or wherein R 1  and R 2  are each independently isopropyl, ethyl, phenyl or tertbutyl; or wherein R 3  is H; or wherein X 1  and X 2  are independently Br or Cl; or wherein Q 2  and Q 4  are H; or wherein Q 1 , Q 3  and Q 5  are each independently isopropyl or tertbutyl; or wherein Q 1 , Q 5  are each independently isopropyl or tertbutyl and Q 3  is H. 
     
     
         28 - 33 . (canceled) 
     
     
         34 . The iron complex of  claim 25 , wherein the complex is represented by the following structures: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         35 . A compound represented by the structure of formula B1 or its isomers: 
       
         
           
           
               
               
           
         
         R 1  and R 2  are each independently linear or branched alkyl, cycloalkyl, heterocyclyl, alkylcycloalkyl, alkylaryl, or alkylheterocyclyl; 
         R 3  is H, D, linear or branched alkyl; 
         Q 1 , Q 2 , Q 3 , Q 4  Q 5  or Q 6  are each independently H, linear or branched alkyl, aryl, heterocyclyl, alkylcycloalkyl, alkylaryl, alkylheterocyclyl, halide, nitro, amide, ester, cyano, alkoxy, NH 2 , aminoalkyl or arylamino; 
         wherein at least one of Q 1 -Q 5  is alkyl; and 
         n is an integer between 1 and 3. 
       
     
     
         36 . The compound of  claim 35 , wherein the compound is represented by the following structures: 
       
         
           
           
               
               
           
         
       
     
     
         37 . The method of  claim 13 , wherein said polymerization is conducted in the presence of an olefin (R—CH═CH 2 , wherein R is substituted or unsubstituted-aryl, phenyl, heteroaryl, alkyl, cycloalkyl or heterocycloalkyl). 
     
     
         38 . The method of  claim 37 , wherein the olefin is styrene, wherein said styrene is optionally in an equimolar amount of the cyclic olefin. 
     
     
         39 . (canceled) 
     
     
         40 . The method of  claim 38 , wherein said styrene itself does not undergo polymerization. 
     
     
         41 . The method of  claim 37 , wherein said polymerization produces a polymer that is soluble in an organic solvent. 
     
     
         42 . (canceled) 
     
     
         43 . The method of  claim 38 , wherein said method produces a polymer capped by CH-Ph (of styrene). 
     
     
         44 . The method of  claim 38 , wherein said polymer comprises a mixture of compounds I, Va, Vb, Vc and Vd: 
       
         
           
           
               
               
           
         
         wherein m 1 , m 2 , m 3 , m 4  and m 5  are each an integer of 2-1,000,000; Q 7  is independently H, linear or branched alkyl, aryl, heterocyclyl, alkylcycloalkyl, alkylaryl, alkylheterocyclyl, Si(alkyl) 3 , halide, nitro, amide, ester, cyano, alkoxy, NH 2 , aminoalkyl or arylamino; and 
         o is an integer between 1-3.